Vat dyestuffs of the anthraquinoneacridone series and a process of preparing them



Patented Jan. 39, 1934 UNITED This invention relates to new vatdyestuffs and a process of preparing them.

More particularly it relates to new, clear yellowish-green togreenish-blue or violet vat dyestuffs of good fastness properties whichare derived from 4- or 5-aminoanthraquinone-2.l-acridone of thefollowing formula:

res Pew OFFICE VAT DYESTUFFS OF THE ANTHRAQUINONE- ACRIDONE SERIES AND APROCESS OF PREPARING THEM Georg Kranzlein, Heinrich Vollmann, andHermann Boedeker, Frankfort on the Main- Hochst, am? Hans Becker,Hofheim in Taunus, Germany, assignors to General Aniline Works, Inc.,New York, N. Y., a corporation of Delaware No Drawing. Application April4, 1932, Serial No. 603,202, and in Germany April 24. 1931 wherein oneof the Bs represents one of the univalent residues of the followingformulae:

4 Claims.

wherein one B stands for hydrogen and the other R for a NHz-group.

The new vat dyestuffs are obtainable by caus- I I ing a compound ofstitution product thereof to react with a halogenated aromatic oraromatic-aliphatic ketone or a poly-ketone having a chainor cyclicstructhe above formula or a sub- O and the other B stands for the sameresidue or hydrogen or halogen and A represents one of the bivalentresidues of the following formulae:

ture but no quinone character, the reaction occurring between the aminogroup of the one compound and the halogen atom of the other compound.

The reaction is advantageously carried out in quired, to the boilingpoint of the diluent.

When using a ketone containing 2 halogen atoms, it is possible toconduct the reaction so that 1 mol or 2 mols of the aoridone compound ofthe above formula react with 1 mol of the haloge- In some cases thereaction occurs in such a way that besides the double connated ketone.

densation product tained a halogen containing primary condensationproduct.

The new products obtainable according to this invention may becharacterized by the following general formula:

Those of the dyestuffs which are obtainable from 2 mols of aminoacridoneand one mol of a dihalogenketone of the type ofp.p-dihalogenbenzophenone are particularly distinguished by a goodaflinity for the fiber.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight:

there is simultaneously ob- (l) parts of 4.4-dibrombenzophenone, 122parts of 4 aminoanthraquinone 2.1 acridone, 120 parts of sodiumcarbonate and 10 parts of copper acetate are heated to boiling for 6-7hours in 3000 parts of nitrobenzene, while well stirring. The reactionproduct, during the boiling operation, precipitates for the greatestpart in the form of crystals and, after the reaction is completed, isfiltered by suction from the hot nitrobenzene mother lye. In order toremove the by-products, the mass remaining on the filter may be washedwith alcohol and hot water or it may be steamdistilled. The dyestuffwhich is obtained in the form of a dark-green, crystalline powdercrystallizes from nitrobenzene in the form of green needles anddissolves in concentrated sulfuric acid to a brownish-orange solution.It dyes the vegetable fiber from a violet-red vat clear, yellowish-greentints of good fastness properties. The dyestufi has the followingprobable formula:

HN NH /O/ Y From the above mentioned nitrobenzene mother lye a dyestuifcontaining bromine may be obtained which probably has been formed bycondensation of only one mol of l-arninoanthraquinone-2.1-acridone withlmol of l.4.--dibrombenzophenone.

Instead of the dibromo-ketone there may be used in the above examplewith the same good result the corresponding dichlorobenzophenone.

By causing in an analogous manner 3.3'-dibrombenzophenone to act upon4-aminoanthraquinone-2.1-acridone, a green dyestuif of a considerablymore bluish-hue is obtained.

(2) 100 parts of 1.4-di-(para-brombenzoyl) benzene (obtainable fromterephthaloyl chloride and brombenzene, melting at 265 C.), 130 parts of4 amino anthraquinone 2.1 acridone, 160 parts of sodium carbonate and'10 parts of copper oxide are :heated to boiling in 2500 parts ofnaphthalene. The color of the melt which is at first blue, after sometime, turns green. The reaction finished, the whole is diluted with. hotnitrobenzene, allowed to cool to about 100 C. and filtered with suction.The product is worked up as described in Example 1. The dyestuif thusobtained in the form of shimmering green needles dyes cotton from aviolet-red vat intense yellowish-green tints of good fastnessproperties. The dyestuff has the following probable formula:

(3) By causing to react, in a manner analogous to that described in thepreceding examples, 20 parts of l-amino-anthraquinone-2.l-benzene-3.5'dichloro-acridone with 14 parts of parabrombenzophenone, a dyestuffis obtained which crystallizes in the form of bluish-green needles. Itdyes cotton from a violet-brown vat intense green tints. The dyestufihas the following probable formula:

u l co /1\ A -Q- -O (4) 90 parts of 2.7-dibromfiuorenone and 150 partsof 4-amino-2.1anthraquinoneacridone are heated to boiling for 1% hourswhile adding 150 parts of sodium carbonate and 10 parts of copperacetate in 3000 parts of nitrobenzene. The condensation product whichprecipitates in the form of crystals is worked up as indicated inExample 1. The dyestuir yields from a violet-red vat yellowish-greendyeings. It has the following probable formula:

f I 09 II I O NH- especially of good fastness to water-drops.

dyestuff has the following probable formula:

" red-violet tints.

formula:

L NH

We claim:

The reaction mass 1. Ihe compounds of the following general formula:

wherein one of the Bs stands for one of the EN 1 C monovalent residuesof the following formulae:

The and the other B stands for the same residue or hydrogen or halogenand wherein A stands for one of the bivalent residues of the followingformulse:

said compounds being clear yellowish-green to greenish-blue or violetvat dyestuffs of good fastness properties.

2. The compounds of the following general formula:

wherein one of the Bs stand for one of the monovalent residues of thefollowing formula:

and the other B stands for the same residue or hydrogen or halogen andwherein A stands for the bivalent residue of the following formula:

said compounds being clear yellowish-green to greenish-blue or violetvat dyestuffs of good fastforming a dark-green crystalline powder,crystallizing from nitrobenzene in the form of green needles, dissolvingin concentrated sulfuric acid to a brownish-orange solution and dyeingthe vegetable fiber from a violet-red vat clear yellowish-green tints ofgood fastness properties.

4. The compound of the following probable ness properties. formula:

NH HN (L 3 G Y 0 EN 00 NH 3. The compound of the following probabledissolving in concentrated sulfuric acid to a formula: brownish-yellowsolution and dyeing the vegetable fiber from a red-violet vat violettints of good fastness properties, especially to waterdrops. 0 GEORGKRANZLEIN. HN NH O HEINRICH VOLLMANN. n I 0 00 I 1 HERMANN BOEDEKER.

/ HANS BECKER.

